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Huq, Nabila A. (ORCID:0000000150889758)

Publications and source records attributed to Huq, Nabila A. (ORCID:0000000150889758).

Fuel Property-Informed Process Design for the Direct Catalytic Conversion of Cellulosics

The direct catalytic conversion of cellulosics (DC3) with supercritical methanol presents a promising pathway to completely solubilize woody biomass and produce >60% mass yield of C2-C6 oxygenates for light duty vehicle applications. Although the oxygenate composition can be tuned by modifying catalyst and process conditions, limited efforts to date have examined DC3 fuel properties for light duty fuel applications to iteratively inform conversion process design. In this work, we designed and evaluated multi-component surrogate bioblendstocks that represent major DC3 light oxygenates and refined catalyst formulations and distillation parameters to improve the resulting light duty fuel quality. Surrogate design for this novel fuel production pathway was based on a preliminary product slate that was systematically adjusted to determine impacts on fuel properties of interest including heating value, oxidative stability, and heat of vaporization, among others. The resulting predictions and measurements of these surrogates were then used to inform improvement of conversion process, and specifically, reformulation of the catalyst which resulted in production of a higher energy density fuel product primarily comprised of saturated alcohols. Fuel testing outcomes also informed downstream oxygenate separations requirements. This resulted in the production of a promising DC3 light-duty fuel blendstock with >15% greater energy density relative to ethanol, while maintaining high octane number and octane sensitivity.

BIOMASS FUELS↗

From Atom to Engine: Understanding Fundamental Effects of Structure on Combustion Using Tandem Experiment and Computation

The ability to tie structural features to a fuel candidate’s ignition properties provides a path for rational design of advantaged fuels that facilitate higher-efficiency, lower-emitting combustion in engines. The time evolution of a fuel’s radical population directly correlates with global combustion parameters, and because the generated radicals depend on the initial structure and reaction pathways of the fuel molecule, it follows that the molecular structure of a fuel has a direct impact on this cascade, and therefore salient ignition-tied fuel properties. This work aims to understand the impact of structural features in the context of global combustion properties for direct application to emerging engine technologies. Specifically, we highlight the ability to identify potential fuel blendstocks for specific engine strategies by examining and elucidating the radical cascade tied to ignition. A representative subset of alcohols possessing a variety of structural features (e.g. branching, chain length) was selected for study using a robust combination of experimental and computational methods. The approach begins with identifying short-lived radicals and likely abstraction sites upon pyrolysis in a microreactor coupled with photoionization mass spectrometry for direct detection of product species. In tandem, electronic structure calculations were performed to calculate the relevant potential energy surfaces for fuel pyrolysis as well as the subsequent O2 addition-isomerization reactions, which govern ignition behavior. Furthermore, the theoretical energetic and ro-vibrational data are used to calculate rate constants for direct ignition modeling to explore how structural effects impact NTC behavior. The microreactor data combined with electronic structure theory calculations provide a well-informed picture of the reactions relevant to ignition for each fuel in this study, as well as the most likely radicals generated under engine conditions. This thorough fundamental picture of fuel decomposition and ignition chemistry is used to correlate the observed ignition behavior to molecular structural effects.

advanced biofuels↗

Performance-advantaged ether diesel bioblendstock production by a priori design

Lignocellulosic biomass offers a renewable carbon source which can be anaerobically digested to produce short-chain carboxylic acids. Here, we assess fuel properties of oxygenates accessible from catalytic upgrading of these acids a priori for their potential to serve as diesel bioblendstocks. Ethers derived from C 2 and C 4 carboxylic acids are identified as advantaged fuel candidates with significantly improved ignition quality (>56% cetane number increase) and reduced sooting (>86% yield sooting index reduction) when compared to commercial petrodiesel. The prescreening process informed conversion pathway selection toward a C 11 branched ether, 4-butoxyheptane, which showed promise for fuel performance and health- and safety-related attributes. A continuous, solvent-free production process was then developed using metal oxide acidic catalysts to provide improved thermal stability, water tolerance, and yields. Liter-scale production of 4-butoxyheptane enabled fuel property testing to confirm predicted fuel properties, while incorporation into petrodiesel at 20 vol % demonstrated 10% improvement in ignition quality and 20% reduction in intrinsic sooting tendency. Storage stability of the pure bioblendstock and 20 vol % blend was confirmed with a common fuel antioxidant, as was compatibility with elastomeric components within existing engine and fueling infrastructure. Technoeconomic analysis of the conversion process identified major cost drivers to guide further research and development. Life-cycle analysis determined the potential to reduce greenhouse gas emissions by 50 to 271% relative to petrodiesel, depending on treatment of coproducts.

09 BIOMASS FUELS↗